阅读说明：本技术 用于重整烃的改性的usy沸石催化剂 (Modified USY zeolite catalyst for reforming hydrocarbons ) 是由 奥默·里法·科塞奥格卢 罗伯特·皮特·霍奇金斯 阿里·H·阿尔沙里夫 内田浩二 渡部光则 于 2018-12-05 设计创作，主要内容包括：本发明涉及一种重整催化剂。所述重整催化剂包括重整金属诸如Pt、载体诸如氧化铝载体、和USY沸石,所述USY沸石的铝骨架的一部分被Zr和Ti取代。USY沸石的量不超过5wt％,并且最优选包含2-3wt％的USY沸石。(The present invention relates to a reforming catalyst. The reforming catalyst includes a reforming metal such as Pt, a support such as an alumina support, and USY zeolite having a portion of its aluminum framework substituted with Zr and Ti. The amount of USY zeolite does not exceed 5 wt% and most preferably comprises 2-3 wt% USY zeolite.)

1. A reforming catalyst comprising a reforming metal supported on a support comprising an Ultrastable (US) Y-type zeolite, wherein a portion of the aluminum atoms of the framework of the USY zeolite thereof are substituted with one or more of zirconium, titanium and hafnium atoms.

2. The reforming catalyst for hydrocarbon oil according to claim 1, wherein the zeolite-1 contains 0.1 to 5 mass% of zirconium atoms and titanium atoms, as calculated on the basis of oxides.

3. A reforming catalyst according to claim 1, wherein the support is an alumina or silica-alumina support.

4. A zeolite for a reforming catalyst according to claim 1, wherein the reforming catalyst has:

(a) the lattice constant is 2.425 to 2.450nm,

(b) specific surface area of 600 to 900m²Per g, and

(c)SiO₂with Al₂O₃The molar ratio is 5 to 100.

5. A reforming catalyst according to claim 1, having a specific surface area of 200 to 450m²(ii)/g; and a pore volume of 0.40 to 1.00 ml/g.

6. A reforming catalyst according to claim 1, comprising 0.01-1.0 wt% of a reforming metal.

7. A reforming catalyst in accordance with claim 1, wherein the reforming metal comprises a noble metal.

8. A reforming catalyst in accordance with claim 7, wherein the noble metal is Ru, Rh, Pd, Ag, Os, Ir, Pt, or Au.

9. A reforming catalyst according to claim 8, wherein the noble metal is Pt.

10. A reforming catalyst according to claim 1, comprising less than 50 wt% USY zeolite.

11. A reforming catalyst according to claim 10, comprising 1-10 wt% USY zeolite.

12. A reforming catalyst according to claim 1, comprising 1-5 wt% USY zeolite.

13. The reforming catalyst of claim 1, wherein the Y-type zeolite comprises V, Zn, Ga, Li, Ca, Mg, or a rare earth metal.

14. A process for reforming a hydrocarbon feedstock, the process comprising at a reaction temperature of 430 ℃ to 600 ℃, a pressure of 1 to 50 bar, 0.5 to 5h^-1And a hydrogen feed ratio of from 1:1 to 50:1, with the reforming catalyst of claim 1.

15. The process of claim 14, wherein the reaction temperature is 430 ℃ to 550 ℃.

16. The method of claim 14, wherein the hydrogen feed ratio ranges from 1:1 to 30: 1.

17. The method of claim 14, comprising reforming the feedstock in a fixed bed reactor.

18. The method of claim 17, wherein the fixed bed reactor is a semi-regenerative fixed bed reactor.

19. The method of claim 14, comprising reforming the hydrocarbon feedstock in a cyclic fixed bed reformer.

20. The method of claim 14, comprising reforming the hydrocarbon feedstock in a continuous reformer.

21. The method of claim 17, comprising reforming the catalyst in a catalyst replacement reactor.

22. The method of claim 14, wherein the feedstock has a boiling point of 36-250 ℃.

23. A process for the manufacture of a reforming catalyst according to claim 1, comprising forming a suspension of USY-type zeolite, a binder and a reforming metal, wherein a portion of the aluminium atoms in the framework of the USY-type zeolite have been substituted by zirconium and titanium atoms and/or hafnium.

24. The method of claim 23, wherein the reforming metal is Pt.

25. The process of claim 23, wherein the USY zeolite-containing catalyst is present in an amount less than 50 wt%.

26. The process of claim 25, wherein the USY zeolite-containing catalyst is present in an amount of 5-10 wt%.

27. The process of claim 25, wherein the USY zeolite-containing catalyst is present in an amount of 1-5 wt%.

Technical Field

The invention relates to a catalyst for the catalytic reforming of hydrocarbon oils, said catalyst comprising a framework-substituted zeolite-Y in which zirconium atoms and/or hafnium atoms and/or titanium atoms form part of the framework of an ultrastable Y-type zeolite.

Background

Catalytic reforming is the primary conversion process in refineries and petrochemical industries. The reforming process is a catalytic process that converts low octane naphtha, for example distilled from crude oil, to higher octane reformate for gasoline blending and aromatic-rich reformate for aromatics production. Basically, the process rearranges or recombines the hydrocarbon molecules in the naphtha feedstock and breaks down some of the molecules into smaller molecules. The naphtha feed for catalytic reforming comprises heavy straight run naphtha. The reforming process converts the low octane naphtha to a high octane motor gasoline blend and aromatics rich in benzene, toluene and xylene with hydrogen and liquefied petroleum gas as byproducts. With the rapid increase in demand for aromatics and high octane requirements, catalytic reforming is likely to remain one of the most important unit processes in the petroleum and petrochemical industries. There are various commercial catalytic reforming processes, which will be well known to the skilled person.

In view of the importance of producing useful products from crude oil, it is not surprising that there is a great deal of literature on catalytic reforming processes.

U.S. patent No.4,698,322 to Santilli teaches a reforming catalyst comprising (i) Pt, (ii) an L-type zeolite, and (iii) a "promoter", which can be Fe, Co, or Ti. The ratio of Pt to promoter is less than 10: 1. The "promoter" is not inserted into the zeolite framework, which in any case is different from the USY zeolite. Nor is an adhesive disclosed.

SkeelsU.S. patent No.5,271,761 teaches a Y zeolite molecular sieve. The skilled artisan recognizes that while both USY and Y zeolites have FAU frameworks, they differ in composition and characteristics. The' 761 patent also describes TiO₂、AlO₂And SiO₂And the Si/Ti ratio and the (Si + Al)/Ti ratio, which are outside the scope of those of the invention described herein.

See alsoLawrenceEt al, U.S. patent No.5,690,810, teaches a reforming process using a solid acid, a group III or group IV member of the periodic table, and a group VIII metal deposit. See alsoAl-MuhaishEt al, U.S. patent No.9,499,403,Inuiet al, U.S. patent No.8,008,226 and U.S. patent No.7,700,005.

U.S. patent No.9,512,371 describes the incorporation of Ti into FAU zeolite followed by its use as a hydrocracking catalyst. The Al/Si weight% ratio ranges from 0.14 to 0.35, which is completely outside the scope of the present invention.

In a sense, catalytic hydrocracking can be considered the "opposite" of the reforming process, as in the former, large molecules are broken down ("cracked") into smaller molecules, while reforming converts the molecules by, for example, dehydrogenation, isomerization, alkylation, and cracking reactions that convert the starting materials into high octane containing molecules. Again, the literature on hydrocracking catalysts is extensive and the inventors wish to draw attention to U.S. patent No.9,221,036, which is incorporated by reference in its entirety. The' 036 patent teaches, inter alia, a hydrocracking catalyst in which the USY backbone is partially substituted with one or more of zirconium, titanium, and hafnium. In these catalysts, metals (Ti, Zr, and/or Hf) replace a portion of the aluminum in the aluminum/silica framework and essentially become part of the framework. Methods for making these catalysts and their use are described in the' 036 patent. Examples 1 and 2 below were taken from this patent in practice.

The zeolite based catalyst provides sufficient acidity to function in cracking, which is desirable in hydrocracking. Instead, these reactions are highly undesirable in reforming reactions, and the goal of developing any new reforming catalyst is to reduce the acidity in the catalytic composition.

Further, the characteristic metals used in hydrocracking are Ni, Mo, and W, used alone or preferably in combination. Such metals are avoided in reforming catalysts characterized by the presence of precious metals. Another essential difference is the temperature at which the hydrocracking and reforming reactions operate, the latter reaction type requiring temperatures of 500 c or higher, much higher than those used for hydrocracking.

It is surprising that hydrocracking catalysts can be modified to reforming catalysts in view of the purpose and reagents used for the reforming process and hydrocracking. However, this is the subject of the present invention, which is set forth in the following disclosure.

Detailed Description

The present invention includes a catalyst useful in reforming processes in which an ultrastable Y (hereinafter, "USY") zeolite is subjected to framework substitution to incorporate one or more of zirconium, titanium, and hafnium into its framework, and also impregnated therein with a reforming process metal, such as Pt, Rh, or Pd. Optionally, the reforming catalyst may include or comprise a metal, such as V, Zn, Ga, Li, Ca, Mg, or a rare earth metal.

The USY zeolite, the base component of the catalyst of the invention, comprises from 0.1 to 5 mass% of one or more of Zr, Ti, and Hf, as calculated on the basis of its oxides. The reforming metal is present in an amount of from 0.01 to 1 wt%, preferably from 0.1 to 0.4 wt% of the resulting catalyst composition. The individual feeds of Zr, Ti, and Hf are less than 0.1 wt%, but when combined, total at least 0.1 wt%.

Generally, the catalytic composition includes a binder (e.g., an alumina binder), USY zeolite, and the foregoing metals. The amount of USY-zeolite should not exceed 50 wt% of the total composition, and is preferably 1-10 wt%, more preferably 1-5 wt%, and most preferably 2-3 wt%.